CN103187520A - Piezoelectric device and method of manufacturing piezoelectric device - Google Patents

Piezoelectric device and method of manufacturing piezoelectric device Download PDF

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Publication number
CN103187520A
CN103187520A CN2012104602951A CN201210460295A CN103187520A CN 103187520 A CN103187520 A CN 103187520A CN 2012104602951 A CN2012104602951 A CN 2012104602951A CN 201210460295 A CN201210460295 A CN 201210460295A CN 103187520 A CN103187520 A CN 103187520A
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film
piezoelectric
electrode
layer
piezoelectric film
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CN103187520B (en
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藤井隆满
菱沼庆一
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Fujifilm Corp
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Fujifilm Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/14—Structure thereof only for on-demand ink jet heads
    • B41J2/14201—Structure of print heads with piezoelectric elements
    • B41J2/14233—Structure of print heads with piezoelectric elements of film type, deformed by bending and disposed on a diaphragm
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/704—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1607—Production of print heads with piezoelectric elements
    • B41J2/161—Production of print heads with piezoelectric elements of film type, deformed by bending and disposed on a diaphragm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/1626—Manufacturing processes etching
    • B41J2/1628—Manufacturing processes etching dry etching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/164—Manufacturing processes thin film formation
    • B41J2/1642—Manufacturing processes thin film formation thin film formation by CVD [chemical vapor deposition]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/164—Manufacturing processes thin film formation
    • B41J2/1646—Manufacturing processes thin film formation thin film formation by sputtering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/05—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes
    • H10N30/057—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes by stacking bulk piezoelectric or electrostrictive bodies and electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/06—Forming electrodes or interconnections, e.g. leads or terminals
    • H10N30/067—Forming single-layered electrodes of multilayered piezoelectric or electrostrictive parts
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
    • H10N30/076—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by vapour phase deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/20—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators
    • H10N30/204—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators using bending displacement, e.g. unimorph, bimorph or multimorph cantilever or membrane benders
    • H10N30/2047—Membrane type
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/87—Electrodes or interconnections, e.g. leads or terminals
    • H10N30/871—Single-layered electrodes of multilayer piezoelectric or electrostrictive devices, e.g. internal electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/87—Electrodes or interconnections, e.g. leads or terminals
    • H10N30/877—Conductive materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/14—Structure thereof only for on-demand ink jet heads
    • B41J2/14201—Structure of print heads with piezoelectric elements
    • B41J2/14233—Structure of print heads with piezoelectric elements of film type, deformed by bending and disposed on a diaphragm
    • B41J2002/14258—Multi layer thin film type piezoelectric element
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2202/00—Embodiments of or processes related to ink-jet or thermal heads
    • B41J2202/01—Embodiments of or processes related to ink-jet heads
    • B41J2202/03—Specific materials used

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physical Vapour Deposition (AREA)
  • Particle Formation And Scattering Control In Inkjet Printers (AREA)
  • Piezo-Electric Or Mechanical Vibrators, Or Delay Or Filter Circuits (AREA)

Abstract

A piezoelectric device includes: a substrate; a first electrode which is layered over the substrate; a first piezoelectric film which is layered over the first electrode; a metal oxide film which is layered over the first piezoelectric film; a metal film which is layered over the metal oxide film; a second piezoelectric film which is layered over the metal film; and a second electrode which is layered over the second piezoelectric film.

Description

Piezoelectric device and manufacture method thereof
Technical field
The method that the present invention relates to a kind of piezoelectric device and make this piezoelectric device, and relate more specifically to a kind of piezoelectric device and manufacturing technology thereof that is constituted by piezoelectric film, this piezoelectric device can be used in a plurality of purposes, for example actuator, transducer, power generating device etc.
Background technology
Japanese Patent Application Publication No.2009-139338 disclose a kind of piezoelectric material film by lamination to be used for the structure of pressure sensor.This pressure sensor has the laminated structure of electrode layer, and piezoelectric film alternately is arranged on the substrate, thereby forms by piezoelectric film lamination body two-layer or that multilayer piezoelectric film constitutes.Electrode comprises platinum (Pt) for example, aluminium (Al), molybdenum (Mo), titanium nitride (TiN), ruthenium materials such as (Ru) (among the JP2009-139338 0034 section), and each piezoelectric film forms (among the JP2009-139338 0077 section) by sputtering method.
Japanese Patent Application Publication No.08-116103 discloses a kind of piezo-activator of bimorph structure, and wherein electrode is made of platinum or palladium.This piezo-activator has laminated structure, wherein first piezoelectric material film (zirconia titanate lead (PZT)) lamination is being used as on the platinum electrode of external electrode, as another platinum electrode lamination of interior electrode on a PZT film, and the external electrode lamination of the 2nd PZT film and platinum (0018 section and Fig. 3 among the JP08-116103) thereon.
Japanese Patent Application Publication No.09-181368 discloses a kind of actuator device with laminated structure, its film by for example sputtering method and similar approach form technology alternately lamination piezoelectrics and electric conductor make, and its wiring method is disclosed.In Japanese Patent Application Publication No.09-181368, the general material relevant with the material of electrode (platinum, aluminium, gold or silver) with the material of piezoelectrics described.
Summary of the invention
As mentioned above, known such laminated structure, wherein by sputtering method lamination piezoelectric film, and electrode and piezoelectric film alternately are formed in the layer.Yet, if when using general electrode material and piezoelectric material layer to overstock electrolemma according to prior art, the problem that exists stripping electrode and piezoelectric film also to peel off, and in fact be difficult to form the above-mentioned laminated structure that is constituted by piezoelectric film.
For example, be set under the situation of intermediate layer (interior electrode) at platinum or palladium electrode, as in JP08-116103, when forming piezoelectric film, piezoelectric may be peeled off or break.
As other object lesson, when forming piezoelectric film by the vapour phase epitaxy mode, substrate temperature is set to and is not less than 350 ℃ and is not higher than 650 ℃ (substrate temperature is piezoelectric direct temperature of crystal growth in vapour phase epitaxy), if after forming piezoelectric film, under normal condition, form the electrode of Pt, iridium (Ir) etc., and then form another piezoelectric film, the problem that then exists stripping electrode and piezoelectric film also to peel off at this electrode.
And even situations such as peeling off of mentioning on do not take place, the tack of the film after film forms is also bad, and the durability of device also has problems.Even use the adhesion layer of titanium (Ti) etc. in order to improve tack, the problem that also exists piezoelectric film in fact to peel off.
The present invention is directed to these situation problems and design, its purpose is to provide a kind of piezoelectric device, the tack that this piezoelectric device has strengthened the film in the laminate that forms by a plurality of piezoelectric films of lamination is peeled off preventing, and have high durability and reliability, and be to provide the manufacture method that to make the top piezoelectric device of mentioning.
In order to reach above-mentioned purpose, the present invention relates to a kind of piezoelectric device, comprising: substrate; First electrode of lamination above substrate; First piezoelectric film of lamination above first electrode; The metal oxide film of lamination above first piezoelectric film; The metal film of lamination above metal oxide film; Second piezoelectric film of lamination above metal film; And second electrode of lamination above second piezoelectric film.
According to this aspect of the invention, the metal oxide film of lamination above first piezoelectric film is as diffusion impervious layer, and the diffusion of the oxygen atom from piezoelectric film to metal film and piezoelectric composition is suppressed.Therefore, can stop the structural change of metal film and the reducing of the tack that caused by diffusion, and can obtain between the laminated structure (intermediate layer) of metal oxide film and metal film, to have the piezoelectric film lamination body of firm attachment.
When explaining, term " the A lamination is above the B " is not limited to the direct lamination of A on B and the situation that A contacts with B, and is included in the situation that inserts and puts one or more layers other layer between A and the B, and the A lamination is above the B and have other layer between A and B.
This structure can be made for the such structure of repetition, namely this structure in, the intermediate layer lamination of metal oxide film and metal film above the piezoelectric film and another piezoelectric film lamination above this intermediate layer, thereby three layers of laminations or more multi-layered piezoelectric film.In this case, may be interpreted as " second piezoelectric film " at the piezoelectric film of top layer, and second or more senior piezoelectric film can be interpreted as " second piezoelectric film ".
Preferably, the product of the stress in the intermediate layer that is made of the metal oxide film between first piezoelectric film and second piezoelectric film and metal film and thickness is less than 100N/m 2
According to this aspect of the invention, be suppressed by peeling off of causing of the caused stress of the difference of the thermal coefficient of expansion between piezoelectric film and the intermediate layer.
Preferably, the thickness in intermediate layer is not less than 50nm and less than 250nm.
Consider the diffusion barrier property in intermediate layer, and the inhibition of peeling off to being caused by the caused stress of the difference of the thermal coefficient of expansion between piezoelectric film and the intermediate layer, the thickness setting in intermediate layer is to be not less than 50nm and is preferred less than the structure in the scope of 250nm.
Preferably, each in first piezoelectric film and second piezoelectric film forms by the vapour phase epitaxy method.
By using vapour phase epitaxy method by the sputtering method representative to obtain to have the piezoelectric film of the piezoelectric property of expectation.Further, piezoelectric film can easily be grown on the metal film, and can obtain good film formation.
Preferably, this vapour phase epitaxy method is for forming the sputtering method of crystalization by the enforcement hotting mask.
According to this aspect of the invention, because metal oxide film is as diffusion impervious layer, therefore, can stop when hotting mask forms material composition from the piezoelectric film in the low layer etc. to diffuse into metal film, and can obtain to have the laminated structure of the piezoelectric film of high tack.
Preferably, metal oxide film comprises the oxide of platinum group metal.
Metal oxide film can have for example any oxide of any metal of the platinum group metal of ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and platinum (Pt).
Also preferably, metal oxide film comprises the oxide of titanium family metal.
Metal oxide film can be for example TiO, TiO 2Deng titanium (Ti) oxide, or any oxide of any metal of the titanium family of Ti, zirconium (Zr) and hafnium (Hf) for example.
Preferably, metal film comprises the platinum group metal.
Metal film can comprise various metals, and metal film preferably includes for example metal of the platinum family of Ru, Os, Rh, Ir, Pd, Pt etc.In this case, first electrode and second electrode can comprise the platinum group metal.In addition, this first electrode and second electrode can comprise copper family metal, copper (Cu), silver (Ag) and gold (Au).
Preferably, each in first piezoelectric film and second piezoelectric film is made of perovskite (perovskite) type oxide.
The piezoelectric device of perofskite type oxide has good piezoelectric property, and can be used in for example various purposes of actuator, transducer, power generating device etc.
Preferably, in each of first piezoelectric film and second piezoelectric film, perofskite type oxide has the crystal preferred orientation of (100) or (001).
For the purpose of mentioning above realizing, the invention still further relates to the manufacture method of piezoelectric device, this method comprises: first electrode of lamination first electrode forms step above substrate; First piezoelectric film of lamination first piezoelectric film forms step above first electrode; The metal oxide film of lamination metal oxide film forms step above first piezoelectric film; The metal film of lamination metal film forms step above metal oxide film; Second piezoelectric film of lamination second piezoelectric film forms step above metal film; And second electrode of lamination second electrode forms step above second piezoelectric film.
According to this aspect of the invention, the structural change of metal film can be prevented and the reducing of the tack that caused by diffusion, and the laminated structure of the piezoelectric film of firm attachment can be obtained to have.
Preferably, each in first piezoelectric film formation step and second piezoelectric film formation step comprises the vapour phase epitaxy method.
According to the present invention, can prevent peeling off of film and reducing of tack, they all are the problems that runs in the prior art the laminate, and can form the laminate of a plurality of piezoelectric films.Therefore, can obtain to have the piezoelectric device of high-durability and reliability.
Description of drawings
With reference to accompanying drawing, will explain other purpose and advantage of essence of the present invention and the present invention below, wherein similar Reference numeral is represented same or analogous part in the accompanying drawing, wherein:
Fig. 1 is the cross-sectional view that illustrates according to the structure of the piezoelectric device of embodiment of the present invention;
Fig. 2 A to 2G is the explanatory diagram that illustrates according to the manufacture method of the piezoelectric device of the first embodiment of the present invention;
Fig. 3 is scanning electron microscopy (SEM) image of structure that is illustrated in the laminate of the piezoelectric film that produces among first embodiment;
Fig. 4 is the view that is illustrated in the P-E hysteresis characteristic of the piezoelectric film that produces among first embodiment;
Fig. 5 is the view of X-ray diffraction (XRD) characteristic that is illustrated in the piezoelectric film that produces among first embodiment;
Fig. 6 A to 6M is the schematic diagram that is illustrated in the manufacture process of the piezoelectric device in the second embodiment of the present invention;
Fig. 7 illustrates about the thickness in intermediate layer and the table of the result of the test of the relation between peeling off;
Fig. 8 is the cross-sectional view that is illustrated in the structure of the piezoelectric device in the third embodiment of the present invention;
Fig. 9 provides the figure to the structure of the ink gun of the piezoelectric device in the 3rd embodiment;
Figure 10 is the table that concerns between the direction of the illustration voltage that is applied to the piezoelectric device among the 3rd embodiment and the amplitude;
Figure 11 is the curve of example that the voltage waveform of the electrode that is applied to the piezoelectric device among the 3rd embodiment is shown;
Figure 12 is the table of measurement result that the displacement of the driving example of piezoelectric device and the piezoelectric device in the 3rd embodiment is shown; And
Figure 13 is the cross-sectional view that the structure of the piezoelectric device in the fourth embodiment of the present invention is shown.
Embodiment
＜execution mode 〉
Fig. 1 is the cross-sectional view that the structure of piezoelectric device according to the embodiment of the present invention is shown.Piezoelectric device 10 shown in Fig. 1 has laminated structure, wherein first electrode 14 forms as on the substrate 12 of supporter, first piezoelectric film 16 forms thereon, and metal oxide film 18, metal film 20, second piezoelectric film 22 and second electrode 24 form thereon in layer in this order further.
At this, in Fig. 1 and other accompanying drawing, for convenience of explanation, under situation about suitably changing, draw thickness and the ratio thereof of layer, and needn't be illustrated by reflecting actual thickness and ratio.Further, in this manual, when describing laminated structure, the direction away from the surface of this substrate 12 on the thickness direction of substrate 12 is expressed as " making progress " direction.In Fig. 1, because piezoelectric device 10 is constructed to keeping making under substrate 12 horizontal state layer 14 to 24 by in turn lamination is on the upper surface of substrate 12 that the setting of these layers is with consistent at the upper and lower relation of setting gravity direction (the downward direction among Fig. 1) when being direction down.In this case, the attitude of substrate 12 can be for that tilt or reverse.Even for the lamination direction of the laminated structure of the attitude that depends on substrate 12 needn't with the upper and lower relation of statement laminated structure under the situation consistent based on the direction up and down of gravity direction with obscuring, the direction away from the surface of substrate 12 on the thickness direction of substrate 12 is expressed as direction upwards.For example, even under the situation that the upside in Fig. 1 and downside are inverted, be formed on by first electrode 14 above the upper surface of substrate 12, and the such statement above the upper surface of first electrode 14 of first piezoelectric film, 16 laminations is described.
Piezoelectric device 10 shown in Fig. 1 has laminated structure, wherein two piezoelectric films (first piezoelectric film 16 and second piezoelectric film 22) and 26 laminations of the intermediate layer between them together.Intermediate layer 26 has the laminated structure of metal oxide film 18 and metal film 20.First electrode 14 be arranged on two piezoelectric films 16 and 22 below, and second electrode 24 is arranged on the top surface.
Though in this example two piezoelectric films 16 and 22, in enforcement of the present invention, also can insert and put intermediate layer (each is corresponding to the intermediate layer 26 among Fig. 1) simultaneously by the three or more piezoelectric film of lamination.In this case, intermediate layer (corresponding to the intermediate layer 26 among Fig. 1) forms second electrode 24 in the alternate figures 1, thereby forms the alternately laminated structure of lamination of piezoelectric film and intermediate layer.Suppose that piezoelectric film is n (wherein n is the integer greater than 1) by the progression of lamination (lamination number), then with (n-1) layer formation intermediate layer.Further, second electrode, second electrode 24 among Fig. 1 for example is formed on the piezoelectric film of (n layer) of top layer.
The material of substrate 12 does not have particular determination, and can use various materials, for example silicon (Si), glass, pottery etc.
First electrode 14 can be made of the material of for example platinum (Pt), aluminium (Al), molybdenum (Mo), titanium nitride (TiN), ruthenium (Ru), gold (Au), silver (Ag) etc.Preferably, first electrode 14 comprises platinum group metal (Ru, Rh, Pd, Os, Ir, Pt).In order to improve the tack with substrate 12, also preferably, this first electrode 14 has Ti or TiW (titanium-tungsten) adhesion layer.Still more preferably, first electrode 14 has the adhesion layer that is arranged on the substrate 12 and the laminated structure that is arranged on the platinum group metal layer on the adhesion layer.
Second electrode 24 can be by constituting with first electrode, 14 similar various materials.Preferably, second electrode 24 comprises platinum family or copper family (Cu, Ag, Au) metal.Further preferably, second electrode 24 has Ti or TiW adhesion layer and the laminated structure that is arranged on the platinum group metal layer on the adhesion layer.This first electrode 14 and second electrode 24 can be made of identical materials, or can be made of different materials.For example, can be that first electrode 14 has the laminated structure of TiW/Pt and second electrode 24 has the laminated structure of TiW/Au.
Metal oxide film 18 is as diffusion impervious layer, and it stops from the oxygen atom of the piezoelectric film 16 of ground floor or the diffusion of piezoelectric composition.This metal oxide film 18 can be electric conductor or insulator.Preferably, this metal oxide film 18 comprises the oxide of platinum family or titanium family (Ti, Zr, Hf) metal.For example, metal oxide film 18 can (be represented as " IrO by the oxide of Ir x" or " Ir-O "), or the oxide of Ti (for example TiO, TiO 2Deng) constitute.
The metal film 20 that is formed on metal oxide film 18 tops plays the useful effect of piezoelectric film 22 that the mode by vapour phase epitaxy method (sputtering method etc.) is formed the second layer.The piezoelectric film that is used for present embodiment is difficult to be grown in oxide, but is grown on the metal easily.Therefore, preferably, metal film 20 is arranged on the metal oxide film 18, and piezoelectric film (second piezoelectric film 22) is formed on the metal film 20.The material of metal film 20 does not have particular determination, and metal film 20 preferably includes the platinum group metal, for example Ir, Pr etc.
Intermediate layer 26 with laminated structure of metal oxide film 18 and metal film 20 can be used as target.As under the situation of target, preferably, metal oxide film 18 is made of electric conducting material in intermediate layer 26.Be not used as in intermediate layer 26 under the situation of any electrode, metal oxide film 18 can be insulating material.
The structure in intermediate layer 26 can for amorphous or crystal.The surface roughness of the film in intermediate layer 26 and structure (cylindrical-shaped structure, nutty structure etc.) distinguishingly do not limit.Further, the orientation of the crystal in intermediate layer 26 and preferred orientation degree are unqualified.Preferably, intermediate layer 26 comprises oxide; But, also can comprise nitrogen.
Each of first piezoelectric film 16 and second piezoelectric film 22 all is that crystallization forms by the rising substrate temperature when the film by the vapour phase epitaxy method forms.The material of first piezoelectric film 16 and second piezoelectric film 22 does not have particular determination, so long as the oxide piezoelectric body gets final product.First piezoelectric film 16 can be constituted or can be made of different materials with second piezoelectric film 22 by identical materials.
＜causal investigation to peeling off 〉
The inventor investigates the electrode that takes place when the piezoelectric film of making prior art and the laminate that electrode replaces lamination and the reason of peeling off of piezoelectric film, under film formation temperature during concurrent present formation piezoelectrics, oxygen atom and piezoelectric composition are (for example, lead under the situation of PZT material (Pb) etc.) diffuse into electrode from piezoelectric, thus cause the structural change of electrode material and tack reduce cause peeling off.Then, the inventor finds, in order to stop the device of peeling off to obtain to have high durability of electrode and piezoelectric film, hinder (stopping) to be formed on piezoelectric composition in the piezoelectric film on the substrate to diffuse into electrode layer be useful, and stop that the diffusion of oxygen atom is even more important.
Based on above mentioned knowledge, in embodiments of the present invention, at the piezoelectric film (first piezoelectric film 16) that forms ground floor afterwards, metal oxide film 18 as diffusion impervious layer is formed on piezoelectric film 16 tops of this ground floor, and is stopped the diffusion of the piezoelectric film (first piezoelectric film 16) from this ground floor by metal oxide film 18.Further, metal film 20 is formed on metal oxide film 18 tops, and the piezoelectric film of the second layer (second piezoelectric film 22) is formed on metal film 20 tops.In other words, the intermediate layer with laminated structure of metal oxide film and metal film is interposed between the piezoelectric film of the piezoelectric film of ground floor and the second layer, and piezoelectric film is arranged in the therebetween layer in intermediate layer.By the step of mentioning above repeating, can guarantee firm tack simultaneously by the lamination piezoelectric film.
＜the first embodiment 〉
Fig. 2 A to 2G is the view that illustrates according to the manufacture process of the piezoelectric device of the first embodiment of the present invention.
Step 1: at first, preparation silicon (Si) substrate 30 (Fig. 2 A).At this, show this example and use bulk silicon substrate (silicon wafer); Yet, also can use the substrate of silicon on insulated substrate (SOI).
Step 2: form the TiW film of 20nm thickness on the surface of Si substrate 30 (upper surface among Fig. 2 B) by sputtering method, and form the Ir film of 150nm thickness thereon.Thereby form the lower electrode 32 of laminated structure of the Ir film of TiW film with 20nm and 150nm.
Step 3: thereafter, under 500 ℃ film formation temperature, form the plumbous film 34 of the zirconia titanate that is doped with niobium (Nb) (hereinafter referred to as " PNZT " or abbreviate as " PZT ") (Fig. 2 C) of 2 μ m thickness by sputtering method at lower electrode 32.In the formation of PZT film 34, use radio frequency (RF) magnetic control sputtering device, it is the Ar of 97.5vol% and the O of 2.5vol% that film forms gas 2Mist, target is to have Pb 1.3((Zr 0.52Ti 0.48) 0.88Nb 0.12) O 3The material of component, and film formation pressure is 2.2m Torr.
Step 4: under 350 ℃ film formation temperature, form the Ir-O film 36 (Fig. 2 D) of 50nm thickness at PZT film 34 by sputtering method.
Step 5: the Ir film 38 (Fig. 2 E) that forms the 20nm thickness at this Ir-O film 36.Form intermediate layer or the electrode 40 of the laminated structure with Ir-O film 36 and Ir film 38 thus.
Reactive sputtering method by using the Ir target is with 50% Ar and 50% O 2Mist under the pressure of 0.5Pa, carry out the formation of Ir-O film 36.Further, after forming Ir-O film 36, obtain Ir film 38 by only using Ar gas to form gas as film.
This Ir-O film 36 is as stopping to stop from the lead in the PZT film 34 of ground floor and the diffusion of oxygen.Further, be formed on the resistance that Ir film 38 on the Ir-O film 36 is inserted into to reduce target, and be used for the growth phase of initial (first) PZT film with condition under descend the growth of the PZT film of one deck.In order to improve tack and to reduce resistivity, the film formation temperature of this Ir-O film 36 and Ir film 38 is 350 ℃ in the present embodiment; Yet, also can be room temperature or higher temperature.Test by reality when changing temperature also can obtain identical result.
Step 6: after forming target 40, form the PZT film 44 (Fig. 2 F) of the second layer thereon.The film formation condition is identical with the condition of the PZT film 34 of ground floor, and the thickness of the PZT film 44 of this second layer is about 2 μ m.
Be used for reference, Fig. 3 is illustrated in the PZT film 44 of the second layer by scanning electron microscopy (SEM) image of the laminated structure of the film under the state of step 6 formation.Laminate shown in Fig. 3 obtains to 6 by step 1.As shown in Figure 3, two PZT films 34 and 44 and the target between them 40 must be had firm tack by lamination, and obtain the good laminate do not peeled off.
Step 7: afterwards, upper electrode 46 is formed on the PZT film 44 of the second layer (Fig. 2 G).This upper electrode 46 is constructed in the mode identical with lower electrode 32, so that form the TiW film of 20nm thickness by sputtering method, and the Ir rete is long-pending thereon to form the thickness of 150nm.Upper electrode 46 forms the laminated structure of the Ir film of TiW film with 20nm and 150nm thus.Therefore, obtain to have a laminated structure piezoelectric device 50 shown in Fig. 2 G.At this, can partly remove the back side (lower surface) of the Si substrate 30 among Fig. 2 G by etching etc.
Structure among＜Fig. 2 G and the corresponding relation of the structure among Fig. 1 〉
Si substrate 30 among Fig. 2 G is corresponding to the substrate 12 among Fig. 1.Lower electrode 32 among Fig. 2 G is corresponding to first electrode 14 among Fig. 1.PZT film 34 among Fig. 2 G is corresponding to first piezoelectric film 16 among Fig. 1, and the PZT film 44 among Fig. 2 G is corresponding to second piezoelectric film 22 among Fig. 1.Ir-O film 36 among Fig. 2 G is corresponding to the metal oxide film 18 among Fig. 1, and the Ir film 38 among Fig. 2 G is corresponding to the metal film 20 among Fig. 1.Upper electrode 46 among Fig. 2 G is corresponding to second electrode 24 among Fig. 1.
＜hysteresis characteristic 〉
For the piezoelectric device 50 that in first embodiment, obtains, studied between the electrode pair characteristic of the piezoelectrics of (between lower electrode 32 and target 40, and between target 40 and upper electrode 46).Fig. 4 illustrates the hysteresis characteristic of the piezoelectrics (PZT film 34) that are present in the ground floor between lower electrode 32 and the target 40, and the hysteresis characteristic that is present in the piezoelectrics (PZT film 44) of the second layer between target 40 and the upper electrode 46.The longitudinal axis among Fig. 4 is represented electric field, and transverse axis is represented polarization.
As shown in the figure, the piezoelectrics of each layer all show good hysteresis characteristic, and obtain enough piezoelectric properties.Herein, the hysteresis curve of each layer all forms whole shape of moving to right hand lateral deviation, and piezoelectrics are polarized in advance.
＜XRD characteristic 〉
Fig. 5 illustrates the result who analyzes the laminated structure (as shown in Figure 3) of two piezoelectric films that obtain by the mode of X-ray diffraction (XRD) in first embodiment.In Fig. 5, the transverse axis indication angle of diffraction 2 θ, and longitudinal axis indication diffracted intensity.In the analysis of the crystal structure of the mode by X-ray diffraction, the laminate that is made of two piezoelectric films is with the radiation once from the top of X-ray.As directed, the PNZT film that obtains in the present embodiment shows the diffraction pattern that concentrates on to heavens on PNZT crystal face (100) and (200), and is confirmed to be the high orientation piezoelectric film that has as (100) and (001) of crystal preferred orientation.According to the method described in first embodiment, can form the piezoelectric film that has excellent degree of crystallinity and do not have any out-phase well.
＜film formation method 〉
As the film formation method of piezoelectric film, the vapour phase epitaxy method is preferred.Except sputtering method, can variety of methods, for example ion electroplating method, Organometallic Chemistry gas phase (MOCVD) deposition process, pulsed laser deposition (PLD) method etc.Further, also can use other method (for example, sol-gel process etc.) outside the vapour phase epitaxy method.
＜piezoelectric 〉
Preferred piezoelectric comprises the perofskite type oxide (P) of one or more types of being explained by following general formula in the present embodiment:
ABO 3，(P)
Wherein A is A bit element and is at least a element that comprises Pb; B is that the B bit is plain and be selected from least a element in the group that is made of Ti, Zr, V, Nb, Ta, Sb, Cr, Mo, W, Mn, Sc, Co, Cu, In, Sn, Ga, Zn, Cd, Fe and Ni; O is oxygen; And the standard molar ratio of A bit element, B bit element and oxygen is 1: 1: 3, but this molar ratio can depart from this standard molar ratio in the scope that can obtain perovskite structure.
The perofskite type oxide of being explained by above-mentioned general formula can be one of leaded compound, the for example plumbous niobic acid nickel of lead titanates, lead zirconate titanate (PZT), lead zirconates, lanthanium titanate lead, zirconium lanthanium titanate lead, zirconia titanate niobic acid manganese lead, zirconia titanate, zirconia titanate zinc niobate lead etc., perhaps their mixing crystallographic system; Perhaps one of lead-free compound, for example barium titanate, barium strontium titanate, bismuth-sodium titanate, bismuth potassium titanate, sodium niobate, potassium niobate, lithium niobate, ferrous acid bismuth etc., perhaps their mixing crystallographic system.
The perofskite type oxide (PX) that comprises one or more types that are expressed from the next according to the piezoelectric film expectation of present embodiment:
A a(Zr x，Ti y，M b-x-y) bO c，(PX)
Wherein A is A bit element and is at least a element that comprises Pb; M is at least a element that is selected from the group that is made of V, N b, Ta and Sb; Satisfy 0＜x＜b, 0＜y＜b and 0≤(b-x-y) relation; And a: b: c=1: 1: 3rd, standard, but this molar ratio can depart from this standard molar ratio in the scope that can obtain perovskite structure.
Because by general formula recited above (P) or (PX) piezoelectric film that constitutes of represented perofskite type oxide have high piezoelectric strain constant (d 31Constant), therefore, the piezo-activator of the piezoelectric film of mentioning above providing becomes excellent at placement property.In this case, the piezoelectric constant of the piezoelectric film that is made of the represented perofskite type oxide of general formula (PX) becomes and is higher than the piezoelectric constant of the piezoelectric film that is made of the represented perofskite type oxide of general formula (P).
Further, provide by general formula (P) or (PX) piezo-activator of the piezoelectric film that constitutes of represented perofskite type oxide voltage-placement property of in drive voltage range, having excellent linearity.This piezoelectric shows the piezoelectric property useful to enforcement of the present invention.
＜the second embodiment 〉
Fig. 6 A to 6M is the view that the manufacture process of piezoelectric device according to a second embodiment of the present invention is shown.In Fig. 6 A to 6M, represent with identical Reference numeral with those same or analogous parts among Fig. 2 A to 2G, and omit description of them.
Step 1 is to 3: the step 1 shown in Fig. 6 A to 6C to 3 with first embodiment that describes with reference to Fig. 2 A to 2C in step 1 to 3 identical.Omit description of them at this.
Step 4: as shown in Fig. 6 D, with the TiO of 200nm 2Film 60 be formed on the PZT film 34 as insulating barrier.
Step 5:TiO 2Insulating barrier 60 is removed the mode patterning (Fig. 6 E) of other parts to stay the desired region part.The insulating barrier that stays by patterning is expressed as 60A.
Step 6: afterwards, Ir- O film 62A and 62B and Ir film 64A and 64B lamination have on the PZT film 34 of insulating barrier 60A, with the total film thickness (Fig. 6 F) with 150nm.The laminated structure of this Ir-O film and Ir film be formed on that insulating barrier 60A goes up and the zone of removing insulating barrier 60 of PZT film 34 on.Herein, the Ir-O film that is formed on the insulating barrier 60A is represented with 62A, the Ir film that is formed on the Ir-O film 62A represents with 64A, and the Ir-O film that is formed in the zone that does not have insulating barrier 60A on the PZT film 34 represents with 62B, represents with 64B and be formed on the Ir-O film 62B Ir film.
Because Ir-O film 62B and Ir film 64B electric insulation on the Ir-O film 62A on the insulating barrier 60A and Ir film 64A and the PZT film 34 in the zone that does not have insulating barrier 60A are essential, the Ir-O film 62B on the Ir-O film 62A on the insulating barrier 60A and Ir film 64A and the PZT film 34 in not having the zone of insulating barrier and Ir film 64B separate the distance by predetermined insulating regions 66 (Fig. 6 F) definition.The method that is used for separating can be for lifting from method or dry-etching method.Further, consider next step because on the PR this point height of Ir film 64A and 64B closer to each other be favourable, can utilize the highly approximating measure (that is, be used for reducing between Ir film 64A and the 64B perpendicular separation) that makes rightly.
Fig. 6 G illustrates the Ir film 64A that is formed on the insulating barrier 60A and is made into thinlyyer, with as making highly approximating example.Replace this method or with its combination, also can make on the PZT film 34 of Ir film 64B in the zone that does not have insulating barrier 60A thicker.
Insulating barrier 60A shown in Fig. 6 F and the 6G and form thereon Ir-O film 62A and the laminate 70A of Ir film 64A as " intermediate layer ".Further, shown in Fig. 6 H, the electrode layer 70B with laminated structure of Ir-O film 62B in the zone of having removed insulating material and Ir film 64B is the intermediate layer as target.In the following description, for example as shown in Fig. 6 I, electrode layer 70B is intermediate layer 70 with the intermediate layer 70A describe, in general terms with insulating barrier 60A.
Step 7: as shown in Fig. 6 H, the PZT film 44 of the second layer is formed on the intermediate layer 70.The film formation condition of the PZT film 44 of this second layer is identical with the condition of the PZT film 34 of ground floor.
Step 8: afterwards, in the identical mode of describing with reference to figure 6D of step 4, form another TiO at PZT film 44 2 Film 60 is as insulating barrier (Fig. 6 I), and repetition and step 5 are to the identical step of 7 (Fig. 6 E to Fig. 6 H).By repeating with step 4 to form the laminated structure (Fig. 6 J) that intermediate layer 70 and piezoelectric film 44 replace lamination to 7 identical step one or many.
Fig. 6 J is illustrated in the example under the state of the PZT film 74 that forms the 3rd layer.Can form four layers of laminations or more multi-layered PZT film.
The pattern of insulating barrier 60A in intermediate layer 70 forms and alternately change the position so that the direction (position of the extraction electrode of end surfaces) of drawing of electrode alternately changes on the right side with on a left side in electrode layer 70B in each level.
Step 9: then, as the TiO of insulating barrier 60 2Film is formed on the PZT film 74 of top layer (being the 3rd layer in this case), the TiO of formation 2Film is patterned with the position in expectation and stays insulating barrier 60A, and forms upper electrode 82 (Fig. 6 K) afterwards.Thus, the laminate of acquisition as shown in Fig. 6 K.
Step 10: at the laminate among Fig. 6 K, by dry ecthing cutting side wall part forming the laminate 88 (Fig. 6 L) of intended shape, and the surface that thus electrode layer (target) 70B-1 and the 70B-2 in intermediate layer 70 is exposed to sidewall.In Fig. 6 L, the electrode layer that is formed between the PZT film 44 of the PZT film 34 of ground floor and the second layer is expressed as 70B-1, and the electrode layer that is formed between the PZT film 74 of the PZT film 44 of the second layer and the 3rd layer is expressed as 70B-2.
Step 11: afterwards, by sputtering method, form side-wall electrode 84 and 86 (Fig. 6 M) in the lateral parts of the laminate 88 in Fig. 6 L.At this, though Fig. 6 M illustrates sidewall perpendicular to base plan; But, because in step 10 by the actual excision of dry ecthing laminate to have the gradually thin shape that becomes littler towards the top and to have angled side walls, can easily form side- wall electrode 84 and 86 on this angled side walls surface.
Be formed on target (electrode layer 70B-1) and upper electrode 82 that side-wall electrode 84 in the sidewall surfaces of the right-hand side in the laminate 88 among Fig. 6 M connects ground floors.Be formed on target (electrode layer 70B-2) and lower electrode 32 that side-wall electrode 86 in the sidewall surfaces of the left-hand side in the laminate 88 among Fig. 6 M connects the second layers.
Usually, under the situation of the laminate with n lamination electrolemma, this laminate also has the electrode of (n+1) layer, be included in the bottom lower electrode, be interposed between the piezoelectric layer target and at the upper electrode of top surface.Odd electrode is connected to each other by a side-wall electrode (side-wall electrode 84 in the example in Fig. 6 M), and even electrode is connected to each other by another side-wall electrode (side-wall electrode 86 in the example in Fig. 6 M).As mentioned above, the target that is exposed to the end surfaces of laminate is connected to lower electrode 32 or upper electrode 82 by side-wall electrode, thereby and is configured to the electrode of pectination.
In the present example, but when inserting and putting the intermediate layer lamination multilayer piezoelectric film, and can form the piezoelectric device 90 with the laminated structure as shown in Fig. 6 M.The piezoelectric device 90 that obtains can be used as actuator, transducer, has actuator or the piezoelectric generator of transducer.The above-mentioned laminate that is made of piezoelectric film can be used as various purposes.
＜comparative example 〉
As a comparative example, prepare laminate according to following operation.After the Ir of the TiW of 20nm film and 150nm rete amasss on the Si substrate, under 500 ℃ substrate temperature (film formation temperature), form the PZT film of 2 μ m thickness thereon by sputtering method.After film formed, the Ir film of 70nm had been formed directly on the PZT film under 350 ℃.Therefore, the laminate in this comparative example has such structure, has namely omitted the Ir-O film as metal oxide film 18 from the structure (Fig. 1) of first execution mode.
After the target of the Ir film that forms 70nm, the PZT film of the second layer is formed directly on the target.Formation condition is identical with the condition of ground floor, and thick with 2 μ m be that target forms.
Yet, after forming step, film from membrane formation device, takes out sample, and the PZT film of the second layer is in the state of peeling off.This is considered to be caused by the oxidized situation of Ir electrode when forming the PZT film of the second layer, this Ir electrode is chemically changed to change its volume owing to the diffusion from the piezoelectric composition Pb of the PZT film of ground floor, and this PZT film is peeled off from Ir electrode (target).
The target that attempt to produce the Ir film is changed to the scheme of the target of Pt film, and the scheme that forms the Ir electrode after forming as the Ti of adhesion layer or TiW film; Yet, with the peeling off of piezoelectric film of the second layer having taken place with top described identical mode.Further, change to the generation that 50nm, 120nm, 150nm and 250nm carry out same sample by the thickness that the Ir film of target will be used as in the comparative example; Yet, the peeling off of piezoelectric film that the second layer has all taken place in any case.
The thickness in＜intermediate layer (target) and peel off between relation
For the laminate according to present embodiment, the thickness in research intermediate layer and peel off between relation, and obtained result in the table shown in Fig. 7.In this case, " intermediate layer " is arranged on the layer between the piezoelectrics.This intermediate layer can be used as electrode or can be used as insulating barrier.Embodiment A among Fig. 7 to the intermediate layer of E is the layer that comprises as at the metal oxide film 18 described in first embodiment and metal film 20.The intermediate layer can have IrO for example as shown in Figure 1 xThe laminated structure of film and Ir film maybe can have the described for example TiO as Fig. 6 A to 6M 2Insulating material membrane and the laminated structure of the metal film of for example Ir.
At this, test by the thickness in the intermediate layer in the laminated structure that changes example as shown in Fig. 1 to Fig. 5.As in the embodiment A in the table among Fig. 7 to shown in the D, if the thin thickness in intermediate layer (being not more than 200nm) is not then peeled off generation.Yet, if the thickness in intermediate layer becomes as thin as a wafer, for example, under the situation less than 50nm, another problem that for example becomes high relatively as electrode resistance will take place, perhaps stop the characteristic from the diffusion of the PZT of lower floor's (ground floor) to descend.
On the other hand, shown in the comparative example in the table among Fig. 7, the thickness in the intermediate layer is not less than in the structure of 250nm, and top piezoelectrics (second layer) are peeled off.Upper electrode is assumed that the stress that the difference owing to the thermal coefficient of expansion between piezoelectrics and intermediate layer etc. causes peels off.As shown in the embodiment E, in the thickness in intermediate layer is the situation of 200nm, observe the state that part is peeled off, yet can think to provide the situation that in fact allows.The intermediate layer of 200nm thickness therefore think can the permission level threshold value (upper limit).
Based on the top main points of mentioning, preferably, the thickness in intermediate layer is not less than 50nm and is not more than 200nm, more preferably is not less than 50nm and less than 200nm, and further preferably is not less than 50nm and is not more than 150nm.
In the superincumbent description, estimate as parameter by the thickness that uses the intermediate layer; Yet whether stress has the principal element of peeling off.Calculating has the stress in the intermediate layer of the thickness shown in the table among Fig. 7, has in the intermediate layer of 200nm thickness to be approximately 500MPa.In other words, consider the optimum condition in intermediate layer based on the relation between thickness and stress, preferably, the stress in intermediate layer and the product of thickness (stress * thickness) are not more than 100N/m 2In this case, the stress in intermediate layer can be zero.
The product of stress and thickness is considered to not rely on the general index of material.Considering the inhibition of peeling off that the stress that is caused by the difference between the thermal coefficient of expansion is produced and utilizing stops the structure of peeling off that is caused by diffusion (in this structure, the piezoelectric film lamination is on the intermediate layer that comprises the metal oxide film that is used as diffusion impervious layer), more preferably, the product of the stress in intermediate layer and thickness is less than 100N/m 2, more preferably be not more than 75N/m 2At this, the stress in intermediate layer and the product of thickness more little (more close to 0), then the stress influence that is caused by the difference between the thermal coefficient of expansion is more little.Therefore, defining preferred lower limit for the product of the pressure in intermediate layer and thickness has little significance.
＜the three embodiment 〉
Fig. 8 is the view of structure that the piezoelectric device 100 of a third embodiment in accordance with the invention is shown.Fig. 8 illustrates the piezo-activator of diaphragm structure.
According to the technology identical with first embodiment, by on SOI substrate 102, producing piezoelectric device 100 with such sequential laminating lower electrode 114, first piezoelectric film 116, metal oxide film 118, metal film 120, second piezoelectric film 122 and upper electrode 124.
SOI substrate 102 has the structure of lamination, the Si layer 104 as processing layer wherein is set, as the oxide membranous layer (SiO of insulating barrier 2) 108 (BOX layers), and the Si layer 110 that is used as device layer.
Form lower electrode 114 by lamination TiW film on Si layer 110 and Ir film.Piezoelectric film 116 and 122 laminations are inserted the target (intermediate layer) 126 of the laminated structure with metal oxide film 118 and metal film 120 simultaneously on lower electrode 114.The Ir-O film is as the metal oxide layer 118 that is formed on first piezoelectric film 116, and the Ir film is as metal film 120.The intermediate layer 126 that obtains by lamination metal oxide film 118 and metal film 120 is used as target.Two piezoelectric films 116 and 122 are set to have target 126 between them, and by lamination TiW film and Au film, form upper electrode 124 at the upper surface of the piezoelectric film 122 of the second layer.
By the etched wafer structure, stay the thick Si layer 110 (device layer) of 5 μ m as diaphragm, it is by from the rear surface side layer being set, and a part of removing Si layer 104 obtains.In this case, the SiO in staying Fig. 8 2The time, SiO 2Layer 108 is as etching stopping layer, and diaphragm is by SiO 2Layer 108 and Si layer 110 constitute; But, also can be by removing SiO 2Layer 108 and construct this diaphragm.
Under the situation of this example, the piezoelectric film 116 of ground floor and the piezoelectric film 122 of the second layer are made of identical piezoelectric, polarize at thickness direction, and the polarised direction unanimity.The direction vector of the dipole moment that polarised direction is caused by the skew of CHARGE DISTRIBUTION (from negative to positive direction) definition.The polarised direction of first piezoelectric film 116 and second piezoelectric film 122 makes progress.
When with the direction identical with the polarised direction of piezoelectrics piezoelectrics being applied electric field, piezoelectrics will be contracted in the interior (d in surface of diaphragm based on the piezoelectricity transversal effect 31Pattern).Piezoelectric film on being formed on diaphragm be contracted in diaphragm the surface in the time, diaphragm has limited the distortion of piezoelectric film.Therefore, diaphragm deformation is with deflection on thickness direction (bending).
Structure as shown in Figure 8 is applied to for example ink gun.Corresponding with black chamber (balancing gate pit) by the recessed space 130 that etching forms.
The example of ink gun shown in Fig. 9.In Fig. 9, represent with identical Reference numeral with those the same or analogous elements in as shown in Figure 8 the structure and the descriptions thereof are omitted.Ink gun 150 shown in Fig. 9 is constructed so that nozzle plate 152 is bonded to the basal surface of the Si layer 104 of the laminated structure described in Fig. 8.The nozzle bore 154 that is used as the injection tip of China ink (liquid) is formed in the nozzle plate 152.By Piezoelectric Driving, China ink is filled in the space (balancing gate pit) 130, and diaphragm (silicon layer 110) is out of shape with deflection, and the stereomutation of balancing gate pit 130, and spray in pressure change and drops out from nozzles hole 154 thus.
Although not shown among Fig. 9, be formed on silicon layer 104 for the China ink supply flow channel (common feed, independently supplying passage etc.) that China ink is supplied to balancing gate pit 130.Further, in Fig. 9, the example that nozzle plate 152 directly is attached to the lower surface of Si layer 104 is shown; Yet the flow passage plate that forms other flow channel structure can be arranged between Si layer 104 and the nozzle plate 152.
The example of＜driving control 〉
In the piezoelectric device 100 according to the 3rd embodiment shown in Figure 8, therefore because the polarised direction of the piezoelectric film that obtains in Fig. 8 116 and 122 makes progress, it is preferred utilizing the driving method (voltage application method) that concerns between the direction that for example has the voltage that applies as shown in Figure 10 and the amplitude.
Voltage application method 1 among Figure 10 is following scheme: target 126 ground connection, positive voltage (+V 1) be applied to lower electrode 114, and negative voltage (V 2) be applied to upper electrode 124.In this case, be applied to the positive voltage (+V of lower electrode 1) and be applied to the negative voltage (V of upper electrode 2) absolute value be set at be equal to each other and |+V 1|=|-V 2|=20V; Yet the particular value of the voltage that applies is not limited to this example.Further, |+V 1| and |-V 2| can be equal to each other.
Voltage application method 2 among Figure 10 is following schemes: lower electrode 114 ground connection, negative voltage (V 3) be applied to target 126, and have the negative voltage (V bigger than the absolute value of the negative voltage that is applied to target 126 4) be applied to upper electrode 124.At this, example-V 3=-20V and-V 4The situation of=-40V; Yet the particular value of the voltage that applies is not limited to this example.
Voltage application method 3 among Figure 10 is following schemes: upper electrode 124 ground connection, positive voltage (+V 5) be applied to target 126, and have the positive voltage (+V bigger than the absolute value of the positive voltage that is applied to target 126 6) be applied to lower electrode 114.At this, example+V 5=+20V and+V 6The situation of=+ 40V; Yet the particular value of the voltage that applies is not limited to this example.
In in voltage application method 1 to 3 any, satisfy the relativeness of Vtop＜Vmid＜Vbot, wherein Vtop is the current potential of upper electrode, and Vmid is the current potential of target, and Vbot is the current potential of lower electrode.
Figure 11 is illustrated in the current potential of the situation bottom electrode of the example that the voltage application method 1 in the table that utilizes Figure 10 applies as voltage.
Further, by to Figure 10 in table in the similar voltage application method of method 1 under test, measure the displacement on the diaphragm of upper electrode.Driving condition and result thereof shown in the table among Figure 12.In this case, measured displacement is corresponding with the emitted dose in the situation that ink gun is arranged in supposition at this.In other words, the displacement of actuator is more big, and then emitted dose is more big.
As shown in Figure 12, be compared to the situation of the one deck (as single layer) that drives independently in two-layer, the situation bottom offset amount that drives first piezoelectric layer and second piezoelectric layer at the same time is bigger.Be 55.5nm or 56.5nm by one deck of driving in two-layer as the displacement that single layer acquires, and be 95.5nm by driving the two-layer displacement that obtains.Therefore, known to driving one deck in two-layer as the situation of single layer, under two-layer driven situation, obtain the displacement with about 1.7 times amplitude.When the voltage that applies changes, displacement also correspondingly changes, and in any case, compared to driving one deck in two-layer as the displacement of single layer, drives two-layer displacement simultaneously and reaches about twice (about 1.7 times).
In the structure shown in Fig. 8, be earth potential by setting target 126, apply+20V is to lower electrode 114 and apply-and 20V is to upper electrode 124, check the displacement (the deflection deflection of diaphragm 110) of actuator, obtain good displacement, and obtained the displacement of about twice compared to the actuator that is constituted by individual layer PZT film.Can obtain enough performances and be used as ink gun.
＜the four embodiment 〉
Next, the fourth embodiment of the present invention is described.Figure 13 is the view according to the structure of the piezoelectric device of the 4th embodiment.In Figure 13, represent with identical Reference numeral with those the same or analogous parts in the structure shown in Fig. 6 A to 6M and omit explanation to them.
Piezoelectric device 160 shown in Figure 13 has the cantilever design that produces by the laminated structure that forms a plurality of piezoelectric films formations of describing among second embodiment at SOI substrate 162.
SOI substrate 162 has laminated structure, and Si layer 164, oxide membranous layer (SiO as processing layer wherein are set 2) layer 168 and as the Si layer 170 of device layer.SOI substrate 162 is used to substitute Si substrate 30 among second embodiment that describes with reference to Fig. 6 A to 6M at this, and by the technology identical with second embodiment, with piezoelectric film 34,44 and 74 laminations on Si layer 164.Obtain with Fig. 6 M in after the identical laminated structure, remove the part of Si layer 164 by the dorsal part of etching substrates 162, thereby stay the Si layer 170 corresponding with diaphragm.Although in Figure 13, stay SiO 2Layer 168, but also can remove SiO 2Layer 168.
Another plate member (for example silicon substrate) 172 is incorporated into the basal surface of the Si layer 164 that stays by etching, and obtains device 160 with the structure shown in Figure 13.
In the device 160 that obtains, by the vibration of cantilever, make piezoelectric film 34,44 and 74 distortion, and between piezoelectric film 34,44 and 74 each upper and lower electrode, produce voltage.This voltage can output to outside to be used as electric power.In other words, device 160 is as the piezoelectric film generator with the laminated structure that can be used as power generating device.By increasing the lamination quantity of piezoelectric film, can obtain the voltage of higher generation.
＜action effect 〉
Referring to figs. 1 through 13 described, according to the embodiment of the present invention, because can use piezoelectric film in the laminated structure, so can use the piezoelectric film material to realize the effective improvement in performance of piezoelectric device.
For example, for as the piezoelectric device of piezo-activator, have low relatively voltage and can obtain big displacement by applying.Further, alleviate the burden of the control circuit that comprises drive circuit by the reduction of driving voltage, and can realize improvement of low cost, energy-conservation, durability etc.
Further, for as the piezoelectric device of power generating device, the voltage of generating can be increased by the laminated structure that uses piezoelectric film, and the power generation performance of the expectation of practical application can be realized being suitable for.
In addition, for as the piezoelectric device of transducer, the distortion by piezoelectric film can obtain big voltage signal, and can improve the sensitivity of transducer.
＜other application examples 1 〉
For example, in angular transducer, adopt drive actuator (utilizing reverse piezoelectric effect) and be used for the piezoelectrics (utilizing piezoelectric effect) of transducer, and global angle transducer of the prior art is constructed to make these two elements to be installed on the identical plane.
On the contrary, the applied laminate according to the present invention, because the piezoelectric film of ground floor can be used as the piezoelectric film of actuator and the second layer and can be used as transducer (or vice versa), angular transducer can be by realizing to compare littler area with structure of the prior art so.
Aforesaidly can be mounted to compact electronic device with transducer and other the device of littler area structure, for example mobile phone etc.Further, because the quantity available that has in wafer than the device of small size increases, so can realize low cost.
＜other application examples 2 〉
In the piezo-activator of the laminated structure with multilayer piezoelectric film, by the piezoelectrics in each layer of high level control, can realize the control of actuator to a greater degree.For example, be applied to ink gun by the piezo-activator with the top laminated structure of mentioning, and drive control, for example change the quantity of the piezoelectric layer that drives in a plurality of piezoelectric layers, can change the size of the drop that sprays, change jet velocity, or the meniscus that waves meniscus is controlled to and causes the degree that do not spray.
Should understand and the invention is not restricted to disclosed particular form, opposite the present invention covers and falls into as all modifications, alternate configuration and equivalent in the expressed spirit and scope of the invention of claims.

Claims (12)

1. piezoelectric device comprises:
Substrate;
First electrode of lamination above described substrate;
First piezoelectric film of lamination above described first electrode;
The metal oxide film of lamination above described first piezoelectric film;
The metal film of lamination above described metal oxide film;
Second piezoelectric film of lamination above described metal film; And
Second electrode of lamination above described second piezoelectric film.
2. piezoelectric device as claimed in claim 1, wherein, the stress in the intermediate layer that is made of the described metal oxide film between described first piezoelectric film and described second piezoelectric film and described metal film and the product of thickness are less than 100N/m 2
3. piezoelectric device as claimed in claim 2, wherein, the thickness in described intermediate layer is not less than 50nm and less than 250nm.
4. piezoelectric device as claimed in claim 1, wherein, each in described first piezoelectric film and described second piezoelectric film forms by the vapour phase epitaxy method.
5. piezoelectric device as claimed in claim 4, wherein, described vapour phase epitaxy method is to form the sputtering method that carries out crystalization by implementing hotting mask.
6. piezoelectric device as claimed in claim 1, wherein, described metal oxide film comprises the oxide of platinum group metal.
7. piezoelectric device as claimed in claim 1, wherein, described metal oxide film comprises the oxide of titanium family metal.
8. piezoelectric device as claimed in claim 1, wherein, described metal film comprises the platinum group metal.
9. piezoelectric device as claimed in claim 1, wherein, each in described first piezoelectric film and described second piezoelectric film is made of perofskite type oxide.
10. piezoelectric device as claimed in claim 9, wherein, in each of described first piezoelectric film and described second piezoelectric film, described perofskite type oxide has the crystal preferred orientation of (100) or (001).
11. the manufacture method of a piezoelectric device, described method comprises:
First electrode of lamination first electrode forms step above substrate;
First piezoelectric film of lamination first piezoelectric film forms step above described first electrode;
The metal oxide film of lamination metal oxide film forms step above described first piezoelectric film;
The metal film of lamination metal film forms step above described metal oxide film;
Second piezoelectric film of lamination second piezoelectric film forms step above described metal film; And
Second electrode of lamination second electrode forms step above described second piezoelectric film.
12. method as claimed in claim 11, wherein, each in described first piezoelectric film formation step and described second piezoelectric film formation step comprises the vapour phase epitaxy method.
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